2,2,2,3a,4,5,6,7a-octachloro-5-methyl-3a,7a,4,5-tetrahydrobenzo[d]-1,3,2-dioxaphosphole | 904704-52-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻烷
• 英文名称: 2,2,2,3a,4,5,6,7a-octachloro-5-methyl-3a,7a,4,5-tetrahydrobenzo[d]-1,3,2-dioxaphosphole
• 英文别名: 5-methyl-2,2,2,3a,4,5,6,7a-octachloro-3a,7a,4,5-tetrahydrobenzo-1,3,2-dioxaphosphol；2,2,2,3a,4,5,6,7a-octachloro-5-methyl-4H-1,3,2λ5-benzodioxaphosphole
• CAS: 904704-52-5
• 化学式: C₇H₅Cl₈O₂P
• 分子量: 435.713
• InChiKey: JCEZBWSTMPAKPV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  18
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,2,2,3a,4,5,6,7a-octachloro-5-methyl-3a,7a,4,5-tetrahydrobenzo[d]-1,3,2-dioxaphosphole 在 水 作用下， 以 丙酮 为溶剂， 反应 96.08h， 生成 1,2,4,4,5,6-hexachloro-5-methyl-3-phosphorylcyclohex-1-ene
  参考文献：
  名称：

  Chlorination of 2,2,2,5-tetrachloro-6-methylbenzo[d]-1,3,2-dioxaphosphole

  摘要：

  An NMR investigation has shown that the reaction of 2,2,2,5-tetrachloro-6-methylbenzo[d]-1,3,2-dioxaphosphole 2 with an excess of molecular chlorine occurs stepwise with high stereo selectivity to give 2,3,4,5,6,6-hexachloro-3-dichlorophosphoryl-5-methylcyclohex-1-ene 4, which then undergoes stabilization via a 3,3-sigmatropic shift of the dichlorophosphonate fragment to give 1,2,4,4,5,6-hexachloro-3-dichlorophosphoryl-5-methylcyclohex-1-ene 5. The configuration of the hydrolysis product of the latter (1,2,4,4,5,6-hexachloro-5-methyl-3-phosphorylcyclohex-1-ene 6) was established by single crystal X-ray diffraction.

  DOI：

  10.1070/mc2005v015n05abeh002170
• 作为产物：
  描述：

  2,2,2,5,-tetrachloro-6-methylbenzo[d]-1,3,2-dioxaphosphole 在 氯 作用下， 以 二氯甲烷 为溶剂， 生成 2,2,2,3a,4,5,6,7a-octachloro-5-methyl-3a,7a,4,5-tetrahydrobenzo[d]-1,3,2-dioxaphosphole
  参考文献：
  名称：

  Chlorination of 2,2,2,5-tetrachloro-6-methylbenzo[d]-1,3,2-dioxaphosphole

  摘要：

  An NMR investigation has shown that the reaction of 2,2,2,5-tetrachloro-6-methylbenzo[d]-1,3,2-dioxaphosphole 2 with an excess of molecular chlorine occurs stepwise with high stereo selectivity to give 2,3,4,5,6,6-hexachloro-3-dichlorophosphoryl-5-methylcyclohex-1-ene 4, which then undergoes stabilization via a 3,3-sigmatropic shift of the dichlorophosphonate fragment to give 1,2,4,4,5,6-hexachloro-3-dichlorophosphoryl-5-methylcyclohex-1-ene 5. The configuration of the hydrolysis product of the latter (1,2,4,4,5,6-hexachloro-5-methyl-3-phosphorylcyclohex-1-ene 6) was established by single crystal X-ray diffraction.

  DOI：

  10.1070/mc2005v015n05abeh002170

文献信息

• Chlorinations of derivatives of 2,2,2-trichlorobenzo-1,3,2-dioxaphospholes
  作者：E. N. Varaksina、V. F. Mironov、A. A. Shtyrlina、A. B. Dobrynin、K. Yu. Cherkin、A. T. Gubaidullin、I. A. Litvinov、A. I. Konovalov

  DOI：10.1134/s1070428008070087

  日期：2008.7

  By P-31, C-13, C-13-H-1}, and H-1 NMR spectroscopy the chlorination of 4- and 5-methyl-2,2,2-trichlorobenzo-1,3,2-dioxaphosphols was shown to provide in quantitative yield 4-methyl-2,2,2,5-tetrachloro- and 6-methyl-2,2,2,5-tetrachlorobenzo-1,3,2-dioxaphosphols. Their hydrolysis led to the formation of difficultly available 4-methyl-5-chloro- and 3-methyl-4-chloro-1,2-dihydroxybenzenes. The structure of the latter compound was established by XRD analysis. The 5-methyl-2-chlorobenzo-1,3,2-dioxaphosphol treated with excess chlorine was converted in succession into 5-methyl-2,3,4,5,6,6-hexachlorocyclohex-1-en-3-yl dichlorophosphate and 5-methyl-1,2,4,4,5,6-hexachlorocyclohex-1-en-3-yl dichlorophosphate. The hydrolysis resulted in 5-methyl-2,3,4,5,6,6-hexachlorocyclohex-2-en-1-yl dihydrophosphate. The configuration of three chiral carbon atoms in the latter was established by XRD study. In the course of the chlorination the aromaticity of the ortho-phenylene fragment was distorted and 3,3-sigmatropic shift of the dichlorophosphoryl group occurred. The reaction with chlorine of 5-tert-butyl-2,2,2-trichlorobenzo-1,3,2-dioxaphosphol and 2,2,2-trichloro-benzo-1,3,2-dioxaphosphol was not selective: The reaction product obtained in excess chlorine transformed on hydrolysis into tetrachloropyrocatechol. Its solvates with water and dioxane were studies by XRD analysis.